Oxidized disulfide oil solvent compositions

ABSTRACT

Oxidized disulfide oil (ODSO) solvent compositions are derived from by-product disulfide oil (DSO) compounds produced as by-products from the generalized mercaptan oxidation (MEROX) processing of a refinery feedstock. The oxidized disulfide oil (ODSO) solvent compositions comprise at least a primary oxidized disulfide oil (ODSO) compound selected from either water soluble or water insoluble oxidized disulfide oil (ODSO) compounds and in some embodiments at least 0.1 ppmw of a secondary oxidized disulfide oil (ODSO) compound that is a water soluble oxidized disulfide oil (ODSO) compound.

RELATED APPLICATIONS

This application is a Divisional application and claims benefit of thepriority of U.S. patent application Ser. No. 16/210,266 filed Dec. 5,2018, the contents of which is incorporated herein by reference in itsentirety.

BACKGROUND OF THE INVENTION Field of the Invention

This invention relates to solvent compositions.

Description of Related Art

A solvent is a compound or composition that can dissolve a solute toproduce a solution. A solvent is usually a liquid, but can be a solid,gas, or supercritical fluid. Solvents have various applications in thechemical, pharmaceutical, oil and gas industries, and are commonly usedin chemical syntheses and purification processes. The amount of solutethat can be dissolved in a certain volume of solvent generally varieswith temperature.

Common uses for organic solvents are in dry cleaning (e.g.,tetrachloroethylene), as paint thinners (e.g., toluene, turpentine), asnail polish removers and adhesive compounds (e.g., acetone, methylacetate, ethyl acetate), in spot removers (e.g., hexane, petrol ether),in detergents (e.g., citrus terpenes) and in perfumes (e.g., ethanol).Water, a polar molecule, is a solvent for other polar molecules and isthe most common solvent used by living things. For example, all of theions and proteins in a cell are dissolved in water contained in thecell.

Solvents can be classified into two broad categories: polar andnon-polar. Generally, the dielectric constant of the solvent provides anappropriate measure of a solvent's polarity. The strong polarity ofwater is indicated by its high dielectric constant of 88 at 0° C.Solvents with a dielectric constant of less than 15 are generallyconsidered to be non-polar. The dielectric constant measures thesolvent's tendency to partly cancel the field strength of the electricfield of a charged particle immersed in it. This reduction is thencompared to the field strength of the charged particle in a vacuum. Thedielectric constant of a solvent can be thought of as its ability toreduce the solute's effective internal charge. Generally, the dielectricconstant of a solvent is an acceptable predictor of the solvent'sability to dissolve common ionic compounds, such as salts. It should benoted that the solubility of a solute is a function of the quantity ofthe solvent that can be dissolved in a specific volume of solvent at aspecified temperature.

The dielectric constant of a solvent is only one measure of the polarityof the solvent, and other more specific measures of polarity exist thatare sensitive to chemical structure. For example, the “Grunwald-WinsteinmY scale” measures polarity in terms of solvent influence on the buildupof the positive charge of a solute during a chemical reaction, asdescribed in Grunwald, E.; Winstein, S. “The Correlation of SolvolysisRates”. J. Am. Chem. Soc. 70 (2): 846, 1948, which is incorporated byreference.

The “Kosower's Z scale” measures polarity in terms of the influence ofthe solvent on UV-absorption maxima of a salt, usually pyridiniumiodide, or the pyridinium zwitterion, as described in E. M. Kosower, J.Am. Chem. Soc., 80, 3253, 1958, “The Effect of Solvent on Spectra. I. ANew Empirical Measure of Solvent Polarity: Z-Values”, which isincorporated by reference.

The “donor number and donor acceptor scale” measures polarity in termsof how a solvent interacts with specific substances, e.g., a strongLewis acid or a strong Lewis base, and is described in Gutmann, V., “TheDonor-Acceptor Approach to Molecular Interactions”, Plenum Press, NewYork and London, 1978, which is incorporated by reference.

The “Hildebrand parameter” is the square root of the cohesive energydensity of the solvent system, as described in Hansen, C. M., Journal ofPaint Technology, Vol. 39, No. 505, February 1967, “The ThreeDimensional Solubility Parameter—Key to Paint Component AffinitiesI.—Solvents, Plasticizers, Polymers, and Resins”, which is incorporatedby reference. The cohesive energy density is the amount of energy neededto completely remove a unit volume of molecules from their neighbors toan infinite separation. The Hildebrand parameter can be used withnonpolar compounds, but it cannot be applied to complex chemistry insolutions.

Polarity can be separated to identify different contributions. ForExample, the “Hansen's parameters” separate the cohesive energy densityinto dispersion, polar and hydrogen bonding contributions, as describedin Hansen, C. M., “The Three Dimensional Solubility Parameter andSolvent Diffusion Coefficient”, Doctoral Dissertation, The TechnicalUniversity of Denmark, Danish Technical Press, Copenhagen, 1967, whichis incorporated by reference.

The polarity, dipole moment, polarizability and hydrogen bonding abilityof a solvent determines what type of compounds it is able to dissolveand with what other solvents or liquid compounds it is miscible.Generally, polar solvents will best dissolve other polar compounds.Similarly, non-polar solvents will best dissolve other non-polarcompounds. Molecules that are highly polar like sugars, e.g., sucrose,or ionic compounds, such as inorganic salts, e.g., sodium chloride,generally dissolve only in very polar solvents like water. In contrasthighly non-polar compounds like oils or waxes will generally dissolveonly in very non-polar organic solvents such as hexane. It follows thatwater (polar) and hexane (non-polar) are not miscible with each otherand will quickly separate into two layers or phases even after beingvigorously shaken or agitated.

Traditional solvents used in industrial aromatic extraction processesinclude glycols: di-, tri- and tetraethyleneglycols, (DEG, TEG andTETRA, respectively); amides: N-methylpyrrolidone (NMP),N-formylmorpholine (NFM); or oxygenated derivatives of sulfur-bearingmolecules such as dimethylsulfoxide (DMSO) or tetramethylenesulfone(sulfolane). These compounds have the general properties of industrialsolvents, including thermal and chemical stability, low toxicity andcorrosivity, ready availability and moderate cost.

It would be highly desirable to provide a solvent composition that hasthe desirable properties and characteristics of known industrialsolvents that can be derived from a low value source that otherwise haslimited utility and whose use or disposal may require installation ofenvironmental safe guards, thereby incurring additional costs that mustbe bet by the refiner.

SUMMARY OF THE INVENTION

In accordance with the present disclosure, new solvent compositions havebeen identified that comprise a mixture of oxidized disulfide oils(ODSOs).

By-product disulfide oil (DSO) compounds derived from the mercaptanoxidative process of a refinery feedstock that have been oxidized havebeen found to constitute an abundant source of the ODSO compounds thatare sulfoxides, sulfonates and sulfones. The recognition of the solventproperties of ODSO compounds derived from the oxidation of the DSOby-products of the mercaptan oxidation employed to reduce or eliminatesulfur compounds from refinery feedstocks transforms the low valueby-product disulfide oils into a valuable industrial commodity that hasutility and applicability in a broad range of fields.

As used herein, the abbreviations of oxidized disulfide oils (“ODSO”)and disulfide oils (“DSO”) will be understood to refer to the singularand plural forms, which may also appear as “DSO compounds” and ODSOcompounds”, and each form may be used interchangeably.

On a global basis, mercaptan oxidation process units, often referred toas MEROX units, are commonly found in refineries and the significantvolume of disulfide oils generated may be blended in low proportionswith fuel oil, or processed in hydrotreating or hydrocracking processunits, or even injected into the ground for disposal. When thedisulfides are added to fuel oil, they are typically burned to producesteam or provide other utilities where they are produced. This use canraise environmental concerns where the combustion gases withsulfur-containing constituents are emitted in the refinery. Thedisulfide oils can undergo hydroprocessing, but hydroprocessing is not afavored method for disposal of waste oil because additional hydrogen isrequired and consumed in the process.

Table 1 includes examples of ODSO compounds produced by the oxidation ofDSO by-product compounds produced in the MEROX sulfur reduction orsweetening process of hydrocarbons containing mercaptans. It will beunderstood that since the source of the DSO is a refinery feedstream,the R substituents vary, e.g., methyl and ethyl subgroups, and thenumber of sulfur atoms, S, in the as-received feedstream can extend to3, i.e., trisulfide compounds. Analyses indicate that any trisulfidespresent are in trace quantities.

TABLE 1 ODSO Name Formula Structure Examples Dialkyl-thiosulfoxide oralkyl-alkane-sulfinothioate (R—SO—S—R)

Dialkyl-thiosulfones or Alkyl-Alkane-thiosulfonate (R—SOO—S—R)

Dialkyl-sulfonesulfoxide Or 1,2-alkyl-alkyl-disulfane 1,1,2-trioxide(R—SOO—SO—R)

Dialkyl-disulfone Or 1,2 alkyl-alkyl-disulfane 1,1,2,2-tetraoxide(R—SOO—SOO—R)

Dialkyl-disulfoxide (R—SO—SO—R)

Alkyl-sulfoxidesulfonate (R—SO—SOO—R)

Alkyl-sulfonesulfonate (R—SOO—SOO—OH)

Alkyl-sulfoxidesulfinate (R—SO—SO—OH)

Alkyl-sulfonesulfinate (R—SOO—SO—OH)

Table 1 includes ODSO compounds that are polar and water-soluble, andalso those that are non-polar and water insoluble. ODSO compounds thatcontain 1 and 2 oxygen atoms are non-polar and water insoluble. ODSOcompounds that contain 3 or more oxygen atoms are water-soluble. Theproduction of either polar or non-polar ODSO compounds is in partdependent on the reaction conditions during the oxidation process.

The ODSO compounds that contain 3 or more oxygen atoms are water solubleover all concentrations and are also oil soluble at relatively lowconcentrations in the range of from 0.1 ppmw to 10 ppmw.

The oxidized disulfide oils from the enhanced MEROX process are highlyeffective as solvents in applications such as aromatic solventextraction and additives to improve the lubricity of transportationfuels. Water soluble ODSO compounds have been found to be highlyselective at removing benzene when compared to traditional solvents,i.e., non-ODSO aromatic extraction solvents, such as sulfolane. The ODSOsolvents can also be used in solvent deasphalting processes and for oildisplacement.

The disulfide oils having the general formula RSSR produced in the MEROXprocess can be oxidized without a catalyst or in the presence of one ormore catalysts to produce a mixture of oxidized disulfide oil (ODSO)compounds. If a catalyst is used in the oxidation of the disulfide oilshaving the general formula RSSR to produce the oxidized disulfide oil(ODSO) compounds, it can be a heterogeneous or homogeneous oxidationcatalyst. The oxidation catalyst can be selected from one or moreheterogeneous or homogeneous catalyst comprising metals from the IUPACGroup 4-12 of the Periodic Table, including Ti, V, Mn, Co, Fe, Cr, Cu,Zn, W and Mo. In certain embodiments, suitable homogeneous catalystsinclude molybdenum naphthanate, sodium tungstate, molybdenumhexacarbonyl, tungsten hexacarbonyl, sodium tungstate and vanadiumpentaoxide. In certain embodiments, suitable heterogeneous catalystsinclude Ti, V, Mn, Co, Fe, Cr, W, Mo, and combinations thereof depositedon a support such as alumina, silica-alumina, silica, natural zeolites,synthetic zeolites, and combinations comprising one or more of the abovesupports. A preferred catalyst is sodium tungstate, Na₂WP₄·2H₂O. Asuitable product is commercially available from, e.g., Sigma-Alrich Co.LLC.

The oxidation to produce the OSDO can be carried out in an oxidationreaction vessel operating at a pressure in the range from about 1 bar toabout 30 bars, or from about 1 bar to about 10 bars, or from about 1 barto about 3 bars. The oxidation to produce the OSDO can be carried out ata temperature in the range from about 20° C. to 300° C., about 20° C. to150° C., about 45° C. to 90° C., about 20° C. to 90° C., about 45° C. to300° C., or about 45° C. to 150° C. [24] The molar feed ratio ofoxidizing agent-to-mono-sulfur can be in the range of from about 1:1 toabout 100:1, about 1:1 to about 30:1, or about 1:1 to about 4:1.

The residence time in the reaction vessel can be in the range of fromabout 5 to 180 minutes, about 15 to 90 minutes, about 15 minutes to 30minutes, about 5 to 90 minutes, about 5 to 30 minutes, or about 15 to180 minutes.

The new solvent composition of the present disclosure comprises at leastone of a primary oxidized disulfide oil (ODSO) compound, selected fromthe group consisting of (R—SO—S—R′), (R—SOO—S—R′), (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH),(R—SO—SO—OH), and (R—SOO—SOO—OH), and mixtures thereof, where R and R′are alkyl groups comprising 1-10 carbon atoms.

In some embodiments, the new solvent composition of the presentdisclosure further comprises at least one of a secondary oxidizeddisulfide oil (ODSO) compound, selected from the group consisting of

(R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH),

(R—SOO—SOO—OH), (R—SO—SO—OH), and (R—SOO—SO—OH), and mixtures thereof,

-   -   where R and R′ are alkyl groups comprising 1-10 carbon atoms,        and wherein the at least one secondary ODSO compound is present        at a concentration of at least 0.1 ppmw.

In the description that follows, the terms “ODSO solvent”, “ODSO solventmixture” “ODSO solvent composition” and “ODSO compound(s)” may be usedinterchangeably for convenience.

Sources of ODSO Compounds

It is known in the art that the presence of mercaptans in petroleumproducts are undesirable because of their unpleasant odor andcorrosivity and also because they degrade the stability of end-productfuels. Processes in oil refineries and natural gas processing plantsthat remove mercaptans and/or hydrogen sulfide (H₂S) are commonlyreferred to as sweetening processes because they result in productswhich no longer have the sour, foul odors of mercaptans and hydrogensulfide. The liquid hydrocarbon disulfides can remain in the sweetenedend products; or they can be used as part of the petroleum refinery ornatural gas processing plant fuel; or they can be subjected to furtherdownstream processing.

The MEROX designation is derived from the mercaptan oxidation step ofthe process. The MEROX process is a proprietary catalytic mercaptanoxidation process widely used in petroleum refineries and natural gasprocessing plants to remove mercaptans contained in end-products such asLPG, propane, butanes, light naphtha, kerosene and jet fuel byconverting them into liquid hydrocarbon disulfides. It is an integratedprocess comprising the mercaptan extraction step in which mercaptansreact with an aqueous caustic solution in the presence of a catalyst toform an alkylthiolate with a base, which is then oxidized in a wet airoxidation step to produce disulfide oils and a regenerated causticsolution that is recycled to the extraction step. The alkalineenvironment required in some versions of the practice of the MEROXprocess is provided by an aqueous solution of sodium hydroxide (NaOH), astrong base, or in other versions of the process, by ammonia, which is arelatively weaker base than sodium hydroxide, but also volatile and mustbe handled with special care due to its irritant and toxicityproperties.

The stepwise reaction schemes for the MEROX process beginning with thetreatment of the mercaptan are as follows:

2RSH+2 NaOH→2NaSR+2 H₂O   (1)

In the above reaction, RSH is a mercaptan and R is an organic group suchas a methyl, ethyl, propyl or other hydrocarbon group. For example, theethyl mercaptan (ethanethiol) has the formula C₂H₅SH.

The catalyst used in some versions of the MEROX process is awater-soluble liquid and in other versions the catalyst is impregnatedonto charcoal granules. The catalyst used in the MEROX process can be anorganometallic compound.

The second step is referred to as regeneration and it involves heatingand oxidizing the caustic solution leaving the extractor. The oxidationresults in converting the extracted mercaptans in the form of alkalimetal thio-alkanes to organic disulfides (RSSR). These disulfides arewater-insoluble liquids that are separated and decanted from the aqueouscaustic solution. The regeneration reaction scheme is as follows:

4NaSR+O₂+2H₂O→2RSSR+4NaOH   (2)

In reactions (1) and (2), R is methyl or a hydrocarbon chain that can bestraight, branched or cyclic. The R chains can be saturated orunsaturated. In most petroleum and diesel fractions, mixtures ofmercaptans will occur such that the R groups in the disulfide oil (RSSR)can be the same or different groups.

The liquid disulfides created by the conversion of the mercaptans do nothave these undesirable characteristics and have been retained in theMEROX treated fuels or removed and used elsewhere in the petroleumrefinery. The MEROX process is generally more economical than acatalytic hydrodesulfurization process and achieves much the same resultfor the mercaptans removal. Economic and practical drawbacks associatedwith hydrodesulfurization processes include additional dedicatedfacilities to which the disulfide compounds must be transferred, use ofexpensive and sensitive catalysts and the treatment and disposal of theby-product sulfur-containing compounds.

BRIEF DESCRIPTION OF THE DRAWINGS

The process for the production and utility of the compositions of thisdisclosure will be described in more detail below and with reference tothe attached figures in which:

FIG. 1 is the experimental GC-MS chromatogram of the non-polar, waterinsoluble solvent composition, referred to below as Composition 1;

FIG. 2A is the experimental ¹H-NMR spectrum of the non-polar, waterinsoluble solvent composition identified as Composition 1;

FIG. 2B is the experimental ¹³C-DEPT-135-NMR spectrum of the non-polar,water insoluble solvent composition identified as Composition 1;

FIG. 3 is the simulated ¹³C-NMR spectrum of dialkyl-thiosulfones;

FIG. 4A is the experimental ¹H-NMR spectrum of the polar, water solublesolvent composition, referred to below as Composition 2;

FIG. 4B is the experimental ¹³C-DEPT-135-NMR spectrum of the polar,water soluble solvent composition identified as Composition 2;

FIG. 5A is the simulated ¹³C-NMR spectrum of a combination of thealkyl-sulfoxidesulfonate (R—SO—SOO—OH) and alkyl-sulfonesulfonate(R—SOO—SOO—OH), and

FIG. 5B is the simulated ¹³C-NMR spectrum of a combination of thealkyl-sulfoxidesulfinate (R—SO—SO—OH) and alkyl-sulfonesulfinate(R—SOO—SO—OH).

DETAILED DESCRIPTION OF THE INVENTION

Compositions comprising mixtures of compounds found to have utility forapplications such as solvents and lubricity additives can advantageouslybe produced by the oxidation of a mixture of disulfide oil (DSO)compounds recovered as a low value by-product of the mercaptan oxidationof a hydrocarbon feedstock.

The oxidation reaction can be conducted in any suitable reaction vessel.Examples of suitable vessels include, but are not limited to, one ormore fixed-bed reactors, ebullated bed reactors, slurry bed reactors,moving bed reactors, continuous stirred tank reactor, and tubularreactors. In embodiments were a fixed bed is used, the reactor can alsocomprise a plurality of catalyst beds.

The oxidation reaction can be conducted in batch mode or continuously.The oxidation reaction is an exothermic reaction that raises thetemperature of the vessel. In certain embodiments, the oxidation can becarried out in a cooled reactor and/or coupled to a heat exchanger tocontrol and maintain the reaction vessel and reactants at apredetermined temperature. If a heat exchanger is coupled to the system,the excess heat can be recovered for later use. It appears that reducingthe temperature of the reaction mixture below a predetermined value, orrange, adversely effects the reaction kinetics and the extent of theexothermic reaction and prevents the reaction from going to completion.

In view of the exothermic nature of the oxidation reaction, the oxidant,e.g., hydrogen peroxide, is added to DSO which is initially at roomtemperature. The temperature of the reaction mixture increases and in anembodiment is maintained at about 80° C. for one hour.

In certain embodiments, the ODSO solvent compounds contain one or morealkyl groups with carbon numbers in the range of from 1 to 10. Incertain embodiments, the number of sulfur atoms in the ODSO compoundscomprising the solvents are in the range of from 1 to 3. In certainembodiments, the number of oxygen atoms in the ODSO compounds is in therange of from 1 to 5. In a preferred embodiment, the number of carbonatoms in the mixture of ODSO compounds comprising the solvent is in therange of from 1 to 20.

The ODSO solvent compositions of the present disclosure can be solubleor insoluble in oil at the effective or working concentrations. The ODSOsolvents produced can be soluble or insoluble in water at the effectiveor working concentrations, depending on the ratio of DSO-to-oxidantpresent in the oxidation reaction.

In accordance with the present disclosure, both water soluble and waterinsoluble ODSO solvents can be produced by controlling the molar ratioof the reactants. For example, an oxidation reaction carried out with ahydrogen peroxide oxidant at a molar ratio of oxidant-to-DSO compounds(calculated based upon mono-sulfur content) of 1.87 produces an ODSOsolvent composition comprising 7% water insoluble ODSO compounds and 93%water soluble compounds. An oxidation reaction carried out at a molarratio of oxidant-to-DSO compounds (calculated based upon mono-sulfurcontent) of 2.40 produces an ODSO solvent composition comprising 1%water insoluble ODSO compounds and 99% water soluble compounds. Anoxidation reaction carried out at a molar ratio of oxidant-to-DSOcompounds (calculated based upon mono-sulfur content) of 2.89 producesan ODSO solvent composition comprising substantially no detectable waterinsoluble ODSO compounds and 100% water soluble compounds.

In these embodiments, any water soluble compounds comprising the solventwill settle to the bottom and form a layer which can be separated fromthe water insoluble compounds. For example, in certain embodiments, asettler tank can be used in batch or continuous mode for separation. Incertain embodiments, two- or three-phase water booth separators known inthe art can be used. In general, as the amount of oxidant that is addedincreases, there is more conversion to the polar, water soluble ODSOsolvent.

The ODSO solvent compositions have boiling points in the range of fromabout 20° C. to 650° C. Water soluble ODSO compounds produced accordingto the present description generally have boiling points in the range offrom about 20° C. to 650° C., while water insoluble ODSO compoundsproduced according to the present description generally have boilingpoints in the range of from about 20° C. to 250° C. In certainembodiments, the ODSO compounds have a dielectric constant that is lessthan or equal to 100 at 0 ° C.

In general, due to the nature of the reaction for synthesizing the ODSOsolvent compositions, even when the ODSO solvent composition iscomprised essentially of water soluble ODSO compounds, trace levels ofwater insoluble ODSO compounds will also be present in the ODSO solventcomposition. Similarly, when the ODSO solvent composition is comprisedprincipally of water insoluble ODSO compounds, trace levels of watersoluble ODSO compounds will also be present in the ODSO solventcomposition. At present, based on experience and knowledge gained fromworking with the present reaction mechanisms, and tests and analysesconducted, the trace levels of either of the respective water insolubleor water soluble ODSO compounds present is in the range of from about0.1 ppmw to 10 ppmw.

EXAMPLES

In the following examples, ODSO compounds were produced by the catalyticoxidation of samples of disulfide oil (DSO) compounds recovered as aby-product of the mercaptan oxidation of a hydrocarbon refineryfeedstock. The feed used in the following examples was composed of 98 W% of C1 and C2 disulfide oils.

The oxidation of the DSO compounds was performed in batch mode underreflux at atmospheric pressure, i.e., at approximately 1.01 bar. Thehydrogen peroxide oxidant was added at room temperature, i.e.,approximately 23° C. and produced an exothermic reaction. The molarratio of oxidant-to-DSO compounds (calculated based upon mono-sulfurcontent) was 2.40. After the addition of the oxidant was complete, thereaction vessel temperature was set to reflux at 80 ° C. forapproximately one hour.

Two immiscible layers formed, one a dark red to brown layer, hereinafterreferred to as Composition 1, and a light-yellow layer, hereinafterreferred to as Composition 2. A separating funnel was used to separateand isolate each of the two layers.

The catalyst used in the examples described below was sodium tungstate.

Example 1

FIG. 1 depicts the experimental GC-MS chromatogram for a non-polar waterinsoluble ODSO solvent (Composition 1) of the present invention. TheGC-MS spectra shows that the following compounds were present in theODSO solvent of Composition 1:

-   -   Peak 1—methylmethanethiosulfonate (H₃C—SOO—S—CH₃);    -   Peak 2—dimethyldisulfoxide (H₃C—SO—SO—CH₃);    -   Peak 3—methylethanethiosulfonate (H₃C—SOO—S—CH₂CH₃);    -   Peak 4—ethylmethyldisulfoxide (H₃C—SO—SO—CH₂CH₃);    -   Peak 5—ethylethanethiosulfonate (H₃CH₂C—SOO—S—CH₂CH₃); and    -   Peak 6—diethyldisulfoxide (H₃CH₂C—SO—SO—CH₂CH₃).

Trace levels of ODSO compounds comprising 3+ oxygen atoms (not shown inthe GC-MS data) are also present. It is clear from the GC-MSchromatogram shown in FIG. 1 that Composition 1 comprises a mixture ofODSO compounds that form the ODSO solvent composition.

FIG. 2A is the experimental ¹H-NMR spectrum for the non-polar waterinsoluble ODSO solvent (Composition 1).

FIG. 2B is the experimental (as distinguished from simulated)¹³C-DEPT-135-NMR spectrum for Composition 1. Composition 1 was mixedwith a CD₃OD solvent and the spectrum was taken at 25° C. The DEPT(Distortionless Enhancement of Polarization Transfer) technique providesreliable information on attached protons in the sample efficiently andwith high selectivity. The DEPT technique is a proton-carbonpolarization transfer method and provides selective identification ofmethyl and/or methylene carbon atoms not available by other analyticaltechniques. In a DEPT-135 spectrum, CH₃ and CH signal peaks showpositive intensities while CH₂ signal peaks are shown as negativeintensities. In the spectrum in FIG. 2B, methyl carbons will have apositive intensity while methylene carbons exhibit a negative intensity.The peaks in the 48-50 ppm region belong to carbon signals of the CD₃ODsolvent.

In order to accurately identify spectral features in ¹³C-135-DEPT-NMRspectra, such as the one in FIG. 2b , and in order to categorize thecorresponding ODSO compounds in the ODSO solvent compositions, ¹³C-NMRpredictions (computational simulations) were carried out using ACDLabssoftware for the following families of possible ODSO compounds:

-   -   dialkyl-thiosulfoxides (R—SO—S—R);    -   dialkyl-thiosulfones (R—SOO—S—R);    -   dialkyl-sulfonesulfoxide (R—SOO—SO—R);    -   dialkyl-disulfone (R—SOO—SOO—R);    -   dialkyl-disulfoxide (R—SO—SO—R);    -   alkyl-sulfoxidesulfonate (R—SO—SOO—OH);    -   alkyl-sulfonesulfonate (R—SOO—SOO—OH);    -   alkyl-sulfoxidesulfinate (R—SO—SO—OH);    -   alkyl-sulfonesulfinate (R—SOO—SO—OH);    -   alkyl-sulfoxidesulfenate (R—SO—S—OH);    -   alkyl-thiosulfonates (R—S—SOO—OH);    -   alkyl-thiosulfinates (R—S—SO—OH); and    -   esters (X—SO—OR or X—SOO—OR, where X═R—SO or R—SOO).

The ¹³C-NMR predictions for the families of possible OSDO compounds weresaved in a database for comparison to experimental data. Since the DSOfeed contained C1 and C2 hydrocarbons, predictions were carried out forODSO solvents where R═C1 and C2 alkyls.

When comparing the experimental ¹³C-135-DEPT-NMR spectrum forComposition 1 (FIG. 2b ) with the saved database of predicted spectra,it was found that the predicted dialkly-thiosulfone (R—SOO—S—R) spectrummostly closely corresponded to the experimental spectrum. This suggeststhat dialkly-thiosulfones (R—SOO—S—R), where R═C1 and C2 alkyls, aremajor compounds in Composition 1. This result is complementary to theGC-MS data shown in FIG. 1. The predicted dialkly-thiosulfone(R—SOO—S—R) spectrum is shown in FIG. 3.

The simulated ¹³C-NMR spectrum in FIG. 3 for Composition 1 correspondswell with the experimental ¹³C-DEPT-135-NMR spectrum, suggesting theidentified compound is present in Composition 1. It is clear from theNMR spectra shown in FIGS. 2a, 2b and 3 that Composition 1 comprises amixture of ODSO compounds that form the ODSO solvent.

Example 2

FIG. 4a is the experimental ¹H-NMR spectrum for a polar water-solubleODSO solvent composition identified as Composition 2.

FIG. 4b is the experimental ¹³C-DEPT-135-NMR spectrum for Composition 2.Composition 2 was mixed with a CD₃OD solvent and the spectrum was takenat 25° C. Similar to the peaks in FIG. 2b , in FIG. 4b methyl carbonshave a positive intensity while methylene carbons exhibit a negativeintensity. The peaks in the 48-50 ppm region belong to carbon signals ofthe CD₃OD solvent.

When comparing the experimental ¹³C-135-DEPT-NMR spectrum of FIG. 4b forComposition 2 with the saved database of predicted spectra, it was foundthat a combination of the predicted alkyl-sulfoxidesulfonate(R—SO—SOO—OH), alkyl-sulfonesulfonate (R—SOO—SOO—OH),alkyl-sulfoxidesulfinate (R—SO—SO—OH) and alkyl-sulfonesulfinate(R—SOO—SO—OH) most closely corresponded to the experimental spectrum.This suggests that alkyl-sulfoxidesulfonate (R—SO—SOO—OH),alkyl-sulfonesulfonate (R—SOO—SOO—OH), alkyl-sulfoxidesulfinate(R—SO—SO—OH) and alkyl-sulfonesulfinate (R—SOO—SO—OH) are majorcompounds in Composition 2. The combined predictedalkyl-sulfoxidesulfonate (R—SO—SOO—OH) and alkyl-sulfonesulfonate(R—SOO—SOO—OH) spectrum is shown in FIG. 5a . The combined predictedalkyl-sulfoxidesulfinate (R—SO—SO—OH) and alkyl-sulfonesulfinate(R—SOO—SO—OH) spectrum is shown in FIG. 5 b.

The simulated ¹³C-NMR spectrum in FIGS. 5a and 5b of Composition 2corresponds well to the experimental ¹³C-DEPT-135-NMR spectrum,suggesting the identified compounds are present in Composition 2. It isclear from the NMR spectra shown in FIGS. 4a, 4b, 5a and 5b thatComposition 2 comprises a mixture of ODSO compounds that form the ODSOsolvent composition.

It is made clear by the results of the above analyses of Compositions 1and 2 that ODSO compounds were present.

Example 3

In order to demonstrate its solvent effect, a comparative example of theuse of the ODSO solvents of the present disclosure in an aromaticextraction process was conducted. An n-dodecane stock solution to whichBTX was added was prepared for use as a feedstock for the extraction ofaromatics using (1) a sulfolane solvent and (2) a water-soluble oxidizeddisulfide oil (ODSO) solvent. The number of carbon atoms in theindividual water soluble OSDO compounds of the ODSO solvent used in thiscomparative example was in the range of from 2 to 4 carbon atoms. Theprepared feedstock contained approximately 5 wt. % of benzene, 5 wt. %of toluene, 5 wt.% of o-xylene, 5 wt. % of m-xylene and 5 wt. % ofp-xylene, as indicated in Table 2.

TABLE 2 Sulfolane Extraction (wt. %) ODSO Extraction (wt. %) NormalizedNormalized Stock Extract Selectivity Stock Extract Selectivity Benzene4.12 0.69 100 4.49 0.26 100 Toluene 4.4 0.37 50 4.95 0.02 7 m- 4.81 0.5872 5.08 0 0 Xylene p-Xylene 4.67 0.21 27 4.95 0 0 o-Xylene 4.66 0.09 124.93 0.06 21

The feedstock and the respective solvents were added to separate flasksand vigorously shaken for 10 minutes at room temperature and atmosphericpressure. After mixing, in both cases two distinct phases separated andwere isolated. The raffinate layer comprised the feedstock with aportion of its aromatics removed. The extract layer comprised thesolvent with the portion of aromatics removed from the feedstock.

Table 2 indicates the results of a GC-MS analysis showing the wt. % ofthe BTX in the extract layer. When the selectivity is normalized to thebenzene extracted, the data indicates that the sulfolane solventextracts some of each of the other components in varying amounts. Incontrast, the results in Table 2 indicate that the water soluble ODSOsolvent has high selectivity for benzene, and significantly lowerselectivity for toluene and o-xylene, with no measurable removal of them- and p-xylene from the prepared feedstock. Koseoglu et al.(SA3207divSA3117)

It is clear from Table 2 that in embodiments where the targeted aromaticcompound is benzene, a preferred aromatic extraction solvent is one or amixture of ODSO compounds used alone, i.e., without other types ofsolvents.

The compositions of the present invention and method for theirpreparation have been described above and characterized in the attachedfigures; however, process modifications and variations will be apparentto those of ordinary skill in the art and the scope of protection forthe invention is to be defined by the claims that follow.

We claim:
 1. An oxidized disulfide oil (ODSO) mixture consisting of twoor more primary oxidized disulfide oil (ODSO) compounds selected fromthe group consisting of (R—SO—S—R′), (R—SOO—S—R′), (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH),(R—SO—SO—OH), and (R—SOO—SOO—OH), and mixtures thereof, and at least oneof a secondary oxidized disulfide oil (ODSO) compound selected from thegroup consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH),(R—SOO—SOO—OH), (R—SO—SO—OH), and (R—SOO—SO—OH), and mixtures thereof,where R and R′ are alkyl groups each of which comprises from 1-10 carbonatoms, and wherein the ODSO compounds in the mixture correspond tooxidized disulfide oils present in an effluent refinery hydrocarbonstream recovered following the catalytic oxidation of mercaptans presentin the hydrocarbon stream.
 2. The ODSO mixture of claim 1, wherein theat least one secondary ODSO compound is present at a concentration of atleast 0.1 ppmw.
 3. The ODSO mixture of claim 1, wherein the mixturecomprises water soluble and water insoluble compounds.
 4. The ODSOmixture of claim 1, wherein the mixture has a dielectric constant thatis less than or equal to 100 at 0° C.
 5. The ODSO mixture of claim 1,wherein the number of oxygen atoms in the two or more primary ODSOcompound is in the range of from 1 to
 5. 6. The ODSO mixture of claim 1,wherein the disulfide oils are oxidized in the presence of a catalyst.7. The ODSO mixture of claim 6, wherein the catalyzed oxidation of thedisulfide oils utilizes one or more heterogeneous or homogeneouscatalysts comprising metals from IUPAC Groups 4-12 of the PeriodicTable.
 8. The ODSO mixture of claim 1, wherein the catalyst is sodiumtungstate.
 9. The ODSO solvent composition of claim 1, wherein theoxidation of the disulfide oils is carried out in an oxidation vesselselected from one or more of fixed-bed reactors, ebullated bed reactors,slurry bed reactors, moving bed reactors, continuous stirred tankreactors, and tubular reactors.
 10. The ODSO mixture of claim 1, whereinthe oxidation of the disulfide oils is carried out at a pressure in therange of from about 1 bar to 30 bars.
 11. The ODSO mixture of claim 1,wherein the oxidation of the disulfide oils is carried out at atemperature in the range of from about 20° C. to 300° C.
 12. The ODSOmixture of claim 1, wherein the oxidation of the disulfide oils iscarried out at a molar feed ratio of oxidizing agent-to-mono-sulfur inthe range of from about 1:1 to about 100:1.
 13. The ODSO mixture ofclaim 1, wherein the oxidation of the disulfide oils is carried out in aresidence time of about 5 to 180 minutes.
 14. The ODSO mixture of claim1, wherein the at least one secondary ODSO compounds are present in anamount in the range of from 0.1 ppmw to 10 ppmw.
 15. The ODSO mixture ofclaim 1, that consists of: